KR20180051515A - Scratch-resistant aqueous 2K PU coating - Google Patents

Abstract

The present invention relates to an aqueous two-component coating composition based on a thioalophanate which preferably contains a hydroxy-functional and / or amino-functional aqueous polymer dispersion and a silane group as a crosslinking agent, To the use of these coating compositions in the manufacture of coatings.

Description

Scratch-resistant aqueous 2K PU coating

The present invention relates to an aqueous two-component coating composition based on a thioalophanate which preferably contains a hydroxy-functional and / or amino-functional aqueous polymer dispersion and a silane group as a crosslinking agent, To the use of these coating compositions in the manufacture of coatings.

Aqueous coating systems are now firmly established as environmentally-friendly alternatives to solvent-borne coating compositions in many applications. In particular, aqueous two-component polyurethane (2K PU) coating materials, including low viscosity hydrophobic or hydrophilic self-emulsifying polyisocyanates as crosslinking component, allow to produce coatings of very good quality.

Polyisocyanate mixtures containing alkoxysilane groups have also been used in aqueous coating systems in the past in order to obtain specific coating properties, for example to improve adhesion, chemical resistance or scratch resistance.

For example, EP-A 0 872 499 describes aqueous two-component polyurethane coating materials comprising compounds having isocyanate groups and alkoxysilyl groups as cross-linking agent components. The use of these specific polyisocyanates leads to coatings with good gloss with improved water resistance.

Hydrophilic modified polyisocyanates containing alkoxysilane groups, which are easier to emulsify, have also been previously identified as crosslinking agent components for aqueous two-component coating dispersions and adhesive dispersions (see, for example, EP-A 0 949 284 ).

In order to improve scratch resistance and chemical resistance of aqueous thermosetting 2K PU automotive clearcoat and topcoat materials, WO 2012/098014 discloses a process for the preparation of an aliphatic and / or cycloaliphatic polyisocyanate, a bis (alkoxysilylalkyl) amine and an N-alkylmono (Alkoxysilylalkyl) amines have been proposed as crosslinker components.

A common trait in all of these polyisocyanate mixtures containing silane groups, which have heretofore been described for use in aqueous coating systems, is that they are composed of a polyisocyanate, which is not modified, and a monofunctional silane containing a group reactive towards isocyanate groups, For example, by the proportional reaction of a mercapto-functional silane, a primary aminoalkylsilane, a secondary N-alkyl-substituted aminoalkylsilane or an alkoxysilane-functional aspartic acid ester.

However, any such reaction inevitably leads to a decrease in the average isocyanate functionality based on the average isocyanate functionality of the starting polyisocyanate used, and this effect becomes apparent as the target silane content in the reaction product increases. In practice, however, polyisocyanate crosslinking agents having very high isocyanate functionality are particularly desirable in the above-mentioned applications, for example, for achieving high network densities, for example, in clearcoat materials.

Moreover, the higher the degree of modification, i. E. The higher the silane group content, the more dramatically the product viscosity increases due to the thiourethane group introduced into the molecule, more particularly the urea group. For this reason, The isocyanate is generally used in a dissolved form using a significant amount of organic solvent as the hydrophilized form with a further reduced functionality.

It is therefore an object of the present invention to provide a polyisocyanate crosslinking agent containing a silane group having a viscosity low enough to be able to be incorporated into the aqueous phase in a finely divided form even if the level of the silane group is high, To provide a novel aqueous coating composition for the production of a scratch resistant coating material.

This object is achieved by providing coating compositions of the present invention, which are described in more detail below.

According to the present invention,

A) at least one polyisocyanate component,

B) at least one aqueous polymer dispersion,

C) optionally at least one catalyst for crosslinking the silane group and

D) optionally further auxiliaries and additives

Wherein the polyisocyanate component A) comprises at least one thioallylphenate containing a silane group of the formula (I): < EMI ID = 1.1 >

here,

R ¹ , R ² and R ³ are the same or different radicals and are saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals each having up to 18 carbon atoms, May contain up to three heteroatoms from the oxygen, sulfur and nitrogen series,

X is a linear or branched organic radical having at least two carbon atoms,

Y is a linear or branched, aliphatic or cycloaliphatic, araliphatic or aromatic radical having up to 18 carbon atoms,

n is an integer of 1 to 20;

The present invention also provides the use of these coating compositions in the manufacture of polyurethane paints and coatings, as well as substrates coated with the coating compositions.

The polyisocyanate component A) of the coating composition of the present invention comprises at least one thiophosphate containing a silane group of the formula (I)

here,

R ¹ , R ² and R ³ are the same or different radicals and are saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals each having up to 18 carbon atoms, May contain up to three heteroatoms from the oxygen, sulfur and nitrogen series,

X is a linear or branched organic radical having at least two carbon atoms,

Y is a linear or branched, aliphatic or cycloaliphatic, araliphatic or aromatic radical having up to 18 carbon atoms,

n is an integer of 1 to 20;

In one preferred embodiment of the present invention, the polyisocyanate component A) of the coating composition of the present invention is comprised of at least one thioalopanate containing a silane group of formula (I).

These thioalophanates containing silane groups are

a) at least one monomeric diisocyanate of formula (II)

b) a mercaptosilane of formula (III)

And an equivalent ratio of isocyanate group to mercapto group of from 2: 1 to 40: 1:

Where Y is a linear or branched, aliphatic or cycloaliphatic, araliphatic or aromatic radical having up to 18 carbon atoms.

Wherein R ¹ , R ² , R ³ and X are as defined above.

The starting compounds a) suitable for preparing the thioalophanates B) containing silane groups can be prepared by any desired method, for example by phosgenation or non-phosgene pathways, for example by urethane cleavage Is any desired diisocyanate having an aliphatic, cycloaliphatic, araliphatic and / or aromatic bonded isocyanate group.

Suitable diisocyanates are, for example, those of the formula (II)

Where Y is a linear or branched, aliphatic or cycloaliphatic radical having 18 or fewer carbon atoms, preferably 4 to 18 carbon atoms, or a linear or branched, aliphatic or cycloaliphatic radical having up to 18 carbon atoms, preferably 5 to 18 carbon atoms Such as, for example, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane ( HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,8- 1,3-diisocyanatocyclohexane, 1,4-diisocyanatohexane, 1,1-diisocyanatohexane, 1,1-diisocyanatomethane, 3,3,5-trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1-isocyanato- 3,5-trimethyl-5-iso (Isophorone diisocyanate; IPDI), 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane, 2,4'- and 4,4'- SOCCIA Ney Todi cyclohexyl methane (H ₁₂ -MDI), 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, 4,4'-dimethyl-3,3'-diimide SOCIETE isocyanato-dish 4,4'-diisocyanato-3,3 ', 5,5'-tetramethyldicyclohexylmethane, 4,4'-diisocyanato-1,1'-bis (cyclohexyl Diisocyanato-3,3'-dimethyl-1,1'-bis (cyclohexyl), 4,4'-diisocyanato-2,2 ', 5,5'- Tetramethyl-1,1'-bis (cyclohexyl), 1,8-diisocyanato-p-menthane, 1,3-diisocyanatoamantane, 1,3- (Isocyanatomethyl) benzene, 1,3- and 1,4-bis (1-isocyanato-1-methylethyl) benzene TMXDI), bis (4- (1-isocyanato-1-methylethyl) phenyl) 1,3-and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, and any desired mixtures of these isomers, diphenylmethane 2,4 ' - and / or -4,4'-diisocyanate and naphthylene 1,5-diisocyanate, and any desired mixtures of said diisocyanates. Furthermore, suitable further diisocyanates can be found, for example, in the literature (Justus Liebigs Annalen der Chemie Volume 562 (1949) pp. 75-136).

Diisocyanate of formula (II) wherein Y is a linear or branched, aliphatic or cycloaliphatic radical having 5 to 13 carbon atoms is particularly preferred as starting component a).

Particularly preferred starting components a) for the process of the invention are 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl- Isocyanatomethylcyclohexane, 2,4'- and / or 4,4'-diisocyanatodicyclohexylmethane, or any desired mixtures of these diisocyanates.

The starting component b) for the preparation of the thioalophanate containing silane groups is any desired mercaptosilane of the formula (III)

here,

R ¹ , R ² and R ³ are the same or different radicals and are saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals each having up to 18 carbon atoms, May contain up to three heteroatoms from the oxygen, sulfur and nitrogen series,

X is a linear or branched organic radical having at least two carbon atoms.

Examples of suitable mercaptosilanes b) are 2-mercaptoethyltrimethylsilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3- 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane and / or 4-mercaptobutyltrimethoxysilane.

Preferred mercaptosilanes b) for the preparation of thioalophanates containing silane groups are those wherein R ¹ , R ² and R ³ are the same or different radicals and are saturated, linear or branched, branched or cyclic, each having up to 6 carbon atoms, Is an aliphatic or cycloaliphatic radical, optionally containing up to three oxygen atoms, and X is a linear or branched alkylene radical having from 2 to 10 carbon atoms.

Particularly preferred mercaptosilanes b) are those in which R ¹ , R ² and R ³ are each an alkyl radical having up to 6 carbon atoms and / or an alkoxy radical containing up to 3 oxygen atoms, with the proviso that the radicals R ¹ , R is of formula (III) is that at least one of ² and R ³ are the alkoxy radical, X is a propylene radical _{(-CH 2 -CH 2 -CH 2)} .

Especially preferred mercaptosilanes b) are those wherein R ¹ , R ² and R ³ are the same or different radicals and each is methyl, methoxy or ethoxy, provided that at least one of the radicals R ¹ , R ² and R ³ is methoxy or (III) wherein X is a propoxy radical, and X is a propylene radical (-CH ₂ -CH ₂ -CH ₂ -).

To prepare the thioalophanate containing the silane group, the diisocyanate a) is reacted with mercaptosilane b) at a temperature of from 20 to 200 DEG C, preferably from 40 to 160 DEG C, in a molar ratio of from 2: 1 to 40: 1, The reaction is carried out while maintaining an equivalent ratio of isocyanate group to mercapto group of from 4: 1 to 30: 1, particularly preferably from 6: 1 to 20: 1, to obtain thioallophanate.

The reaction can be carried out as a thermally induced allophanatization without catalyst. However, preferably a catalyst suitable for accelerating the allophanatization reaction is used. This can be achieved by conventional known allophanatization catalysts, for example metal carboxylates of the type described in GB-A-0 994 890, metal chelates or tertiary amines, or of the type described in US-A-3 769 318 Or strong acid as described, for example, in EP-A 0 000 194.

Suitable allophanatization catalysts are in particular zinc compounds such as zinc (II) stearate, zinc (II) n-octanoate, zinc (II) (II) acetylacetonate, tin compounds such as tin (II) n-octanoate, tin (II) 2-ethyl-1-hexanoate, tin (II) laurate, dibutyl tin Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate or dioctyltin diacetate, zirconium compounds such as zirconium (IV) 2-ethyl-1-hexa Zirconium (IV) neodecanoate or zirconium (IV) acetylacetonate, aluminum tri (ethylacetoacetate), iron (III) chloride, potassium octoate, manganese, cobalt Or nickel compounds, and also strong acids such as, for example, Trifluoroacetic acid, sulfuric acid, hydrogen chloride, hydrogen bromide, phosphoric acid or perchloric acid, or any desired mixtures of these catalysts.

Although less preferred, for preparing thioallophanates containing silane groups, suitable catalysts are also compounds that promote trimerization of isocyanate groups to form isocyanurate structures as well as allophanate reactions. Catalysts of this kind are described, for example, in EP-A 0 649 866 page 4, line 7 to page 5, line 15.

Preferred catalysts for preparing thioalophanates containing silane groups are the zinc and / or zirconium compounds of the kind described above. (II) n-octanoate, zinc (II) 2-ethyl-1-hexanoate and / or zinc (II) stearate, zirconium -1-hexanoate and / or zirconium (IV) neodecanoate is particularly preferably used.

In the preparation of the thioalophanates containing silane groups, these catalysts, if used, are used in amounts of 0.001 to 5 wt%, preferably 0.005 to 1 wt%, based on the total weight of reactants a) and b) And may be added both before the start of the reaction and at any point during the reaction.

The preparation of the thioalophanate containing silane groups is preferably carried out without a solvent. However, optionally, it is also possible to use a suitable solvent which is inert towards the reactive groups of the starting components. Suitable solvents are, for example, conventional paint solvents known per se such as ethyl acetate, butyl acetate, ethylene glycol monomethyl or monoethyl ether acetate, 1-methoxyprop-2-ylacetate (MPA) , 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, white oil, Solventnaphtha, Solvesso®, Isopar®, Nappar®, Varsol® (ExxonMobil Chemical Central Europe, Germany, Cologne, Germany) And Shellsol (Shell Deutschland Oil GmbH, Hamburg, Germany), and also solvents such as propylene glycol diacetate, diethylene glycol dimethyl on Le, dipropylene glycol dimethyl ether, diethylene glycol ethyl and butyl ether is any desired mixture of the acetate, N- methyl-pyrrolidone and N- methyl-caprolactam, or these solvents. These solvents or solvent mixtures preferably have a water content of up to 1.0 wt%, more preferably up to 0.5 wt%, based on the solvent used.

In one embodiment, during the preparation of the thioalophanate containing the silane group, the starting diisocyanate a) or a mixture of the various starting diisocyanates a) is optionally treated with an inert gas such as, for example, under nitrogen, In the presence of a suitable solvent at a temperature of 20 to 100 < 0 > C. Subsequently, a mixture of mercaptosilane b) or a variety of mercaptosilanes is added in the amounts mentioned above, and the reaction temperature for the thiourethanation is optionally adjusted by suitable measures (heating or cooling) from 30 to 120 캜, Lt; RTI ID = 0.0 > 100 C < / RTI > After the thiourethanization reaction, i. E. When the NCO content reached is theoretically equivalent to the complete conversion of the isocyanate group and the mercapto group, the thioalofanation can be carried out, for example, Lt; 0 > C. Preferably, however, a suitable catalyst of the above-mentioned kind is used to accelerate the thioalophanate reaction, and in this case, depending on the nature and amount of the catalyst used, it is preferably from 60 to 140 캜, Temperatures in the range of 70 to 120 占 폚 are sufficient to carry out the reaction.

In another embodiment of the process for preparing a thioalophanate containing silane groups, a catalyst for optional co-use is even incorporated into the diisocyanate component a) and / or the silane component b) before the start of the actual reaction. In this case, the thiourethane group formed as an intermediate undergoes a spontaneous further reaction to provide the desired thioalophanate structure. In this kind of one-step reaction scheme, the starting diisocyanate a) optionally containing a catalyst is reacted with a starting diisocyanate a), optionally in the presence of an inert gas, for example under nitrogen and optionally in the presence of a suitable solvent of the kind mentioned, Is reacted with a silane component b) which is introduced at a temperature in the range from 60 to 140 캜, preferably from 70 to 120 캜, and which optionally contains a catalyst, which is optimal for the phonation.

An alternative option is to add the catalyst to the reaction mixture at any desired time during the thiourethylation reaction. In the case of this embodiment of the process for preparing a thioalophanate containing silane groups, the temperature set for the pure thiourethylation reaction which proceeds before the addition of the catalyst is generally from 30 to 120 캜, preferably from 50 to 100 캜 Range. After the addition of a suitable catalyst, finally, the thioalophanate reaction is carried out at a temperature of from 60 to 140 캜, preferably from 70 to 120 캜.

In the case of the preparation of the thioalophanate containing silane groups, the course of the reaction can be monitored, for example, by determination of the NCO content by titration. When the target NCO content is reached, it is preferred that the thiourethane group formed as an intermediate from the mercapto group of the degree of thioalophanation of the reaction mixture (i.e., component b) and undergoes the reaction to form the thioalophanate group , The percentage of the percentage, calculated from the NCO content) is at least 70%, more preferably at least 90%, very preferably after complete thioalophanatization. In the case of a pure thermal reaction scheme, this can be achieved, for example, by cooling the reaction mixture to room temperature. However, in the case of the preferred co-use of the thioalophanate catalyst of the type mentioned, the reaction is generally stopped by the addition of a suitable catalyst poison, for example an acyl chloride such as benzoyl chloride or isophthaloyl dichloride.

Then, under highly mild conditions, for example at from 100 to 200 DEG C, preferably from 120 to 200 DEG C, preferably at a pressure of less than 1.0 mbar, preferably less than 0.5 mbar, more preferably less than 0.2 mbar, Volatile constituents (excess monomeric diisocyanate, optionally used solvent, and any active catalyst, if no catalyst poisons are used) are removed from the reaction mixture by thin-film distillation at a temperature of from 180 DEG C to 180 DEG C.

The obtained distillate containing any active catalyst, as well as unreacted monomeric starting diisocyanate, as well as any solvent used, if a catalyst poison is not used, can be readily used for regenerative oligomerization.

In another embodiment of the process for preparing a thioalopanate containing silane groups, the volatile components mentioned are selected from the group consisting of aliphatic or cycloaliphatic hydrocarbons, such as pentane, hexane, heptane, Is removed from the oligomerization product by extraction with cyclopentane or cyclohexane.

Regardless of the type of post-treatment, the resulting product generally has a color number of less than 120 APHA, preferably less than 80 APHA, more preferably less than 60 APHA, and from 2.0 to 18.0 wt%, preferably from 7.0 to 17.0 wt %, More preferably 10.0 to 16.0 wt%, based on the total weight of the polyisocyanate. The average NCO functionality is generally from 1.8 to 3.0, preferably from 1.8 to 2.5, more preferably from 1.9 to 2.1, depending on the degree of conversion and the thioalophanate catalyst used.

In addition to the thioalophanate polyisocyanate, the polyisocyanate component A) may optionally additionally optionally also comprise a polyisocyanate having an aliphatic, cycloaliphatic, araliphatic and / or aromatic bonded isocyanate group which may already have a silane group. These additional polyisocyanates are described in more detail in, for example, Laas et al., J. Prakt. Chem. 336, 1994, 185-200), DE-A 1 670 666, DE A 3 700 209, DE-A Isocyanurate, isocyanurate, isobutyraldehyde, isobutyraldehyde, isocyanurate, isocyanurate, isocyanurate, isocyanurate, isocyanurate, isocyanurate, isocyanurate and isobutyrate as described in EP- Known paint isocyanates having a dione, urethane, allophanate, biuret and / or oxadiazinetrione structure and also known paint isocyanates, for example as described in EP-A 1 273 640, WO 2014/086530 or WO 2009/156148 The same reaction product of said polyisocyanate with a compound containing a silane group and being reactive towards isocyanate groups.

Additionally, preferred additional polyisocyanates that may be present in the polyisocyanate component A), in addition to the thioalophanate containing the silane group, are those which, for example, are such that, for example, the polyisocyanate component is incorporated into the aqueous polymer dispersion B) Is any desired hydrophilic modified polyisocyanate, which can make it easier to handle. Suitable hydrophilic modified polyisocyanates for this purpose are, for example, EP-A 0 206 059 and EP-A 0 540 985, EP-A 0 959 087, EP-A 0 486 881 and WO 2005/047357 Or a reaction product of the aforementioned paint polyisocyanate with a hydrophilic polyether alcohol, for example of the kind described in WO 01/88006 or WO 2015/0035673, or a reaction product of the aforementioned polyisocyanate with an aminosulfonic acid, or For example, a blend of this type of polyisocyanate with alkylphenol polyglycol ether phosphates and / or phosphonates or fatty alcohol polyglycol ether phosphates and / or phosphonates, known from WO 97/31960, It is present in neutralized form with tertiary amine.

Particularly preferred further polyisocyanates which may be present in the polyisocyanate component A) in addition to the thioalphonate containing silane groups are those of the abovementioned type, more particularly those having only aliphatic and / or cycloaliphatically bonded isocyanate groups, more particularly PDI, HDI and / or IPDI.

In the coating composition of the present invention, even though these additional polyisocyanates are used in the polyisocyanate component A), it is preferred that the polyisocyanate component A) consisting of at least one thioalphanate containing silane groups and optionally further polyisocyanates Is used in an amount of not more than 70 wt%, preferably not more than 60 wt%, more preferably not more than 50 wt%, based on the total amount.

In blends which are present when the additional polyisocyanate of the kind mentioned is used in combination with the polyisocyanate component A), the very low viscosity of the thioalophanate polyisocyanate containing the silane group allows it to have a generally higher viscosity It serves as a reactive diluent for paint polyisocyanates. Compared to the prior art silane-functional polyisocyanates of the prior art, in comparable silane content, these blends of thiophosphate polyisocyanates containing silane groups and other polyisocyanates have much higher isocyanate content and isocyanate functionality And exhibits an advantage of lower viscosity.

The coating compositions of the present invention comprise as binder component, any desired aqueous polymer dispersion B) preferably having groups reactive with isocyanate groups, more preferably hydroxyl groups and / or amino groups.

Suitable aqueous polymer dispersions B) are all polymer dispersions customary in aqueous 2K PU coating technology. It is also possible, for example, to carry out the processes described in EP-A 0 358 979, EP-A 0 469 389, EP-A 0 496 205, EP-A 0 557 844, EP-A 0 583 728, WO 94/03511, WO Polyurethane resins, polyurea resins, polycarbonate resins or polyesters of the type described in WO 94/28043, WO 94/28043 or WO 95/02005, polyurethane resins, polyurethane resins, Ether resin. It is also possible to use any desired mixtures of any desired hybrid dispersions or various polymer dispersions.

Examples of suitable hydroxy-functional polycarbonate dispersions B ₁ ) are copolymers of olefinically unsaturated monomers having hydroxyl groups in an organic solvent with hydroxyl-free olefinic monomers, neutralization of the incorporated ionic groups , And known so-called secondary polyacrylate dispersions, which can be prepared in a manner known per se by dispersion in water.

Examples of suitable monomers for preparing the secondary polyacrylate dispersions B ₁ ) include, for example, vinyl and vinylidene monomers such as styrene,? -Methylstyrene, o- and / or p- Acrylic acid, acrylonitrile, methacrylonitrile, acrylic acid and methacrylic acid esters of alcohols having up to 18 carbon atoms, such as, for example, styrene, styrene, Acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, , Isooctyl acrylate, 3,3,5-trimethylhexyl acrylate, stearyl acrylate, lauryl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, 4-tert- N-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, , tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, 3,3,5-trimethylhexyl methacrylate, stearyl methacrylate, But are not limited to, acrylic acid, methacrylic acid, lauryl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, norbornyl methacrylate or isobornyl methacrylate, fumaric acid, itaconic acid, Diesters of alcohols having 4 to 8 carbon atoms, acrylamides, methacrylamides, diesters of 2 to 5 carbon atoms Vinyl esters of alkane monocarboxylic acids such as vinyl acetate or vinyl propionate, carboxy-functional radically polymerized monomers such as acrylic acid, methacrylic acid,? -Carboxyethyl acrylate, crotonic acid, fumaric acid, maleic acid Monoalkyl maleates of monoalkyl maleates, hydroxyalkyl esters of acrylic acid and methacrylic acid having 2 to 6 carbon atoms in the hydroxyalkyl radical, such as 2 < RTI ID = 0.0 > -Hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, trimethylolpropane mono- or pentaerythritol mono-acrylate or methacrylate, Hydroxyl monomers containing a seed unit such as, for example, ethylene oxide, propylene oxide or butylene oxide, The addition of rilsan or methacrylic acid, water, and also any desired mixtures of the exemplified monomer.

Further suitable olefinically unsaturated monomers for preparing the secondary polyacrylate dispersions B ₁ ) are vinyl monomers containing alkylene oxide units such as acrylic acid or methacrylic acid and oligoalkylene oxide monoalkyl ethers And also a monomer having an additional functional group such as an epoxy group, an alkoxysilyl group, a urea group, a urethane group, an amide group or a nitrile group, and also a (meth) acrylate monomer having two or more functional groups And / or vinyl monomers such as, for example, hexanediol di (meth) acrylate, which may be used in conjunction with a small amount of, for example, 3 wt% or less based on the sum of the monomers.

Preferred olefinically unsaturated monomers for preparing the secondary polyacrylate dispersions B ₁ ) are methyl methacrylate, styrene, acrylic acid, methacrylic acid, butyl acrylate, butyl methacrylate, ethyl acrylate, tert-butyl acrylate Hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxypropyl methacrylate, Roxybutyl methacrylate.

In the secondary polyacrylate dispersion B ₁ ), the amount of carboxy-functional monomer is from 0.8 to 5 wt%, in particular from 1.2 to 4 wt%, the amount of hydroxy-functional monomer is from 1 to 45 wt% Is 6 to 30 wt%.

Secondary polyacrylate dispersions B ₁ ) suitable for the coating compositions of the present invention are prepared from olefinically unsaturated monomers in the presence of a polymerization initiator known per se. Examples of suitable initiators are peroxy compounds such as diacyl peroxide, alkyl peresters, dialkyl peroxides, peroxydicarbonates, inorganic peroxides or azo compounds.

In principle, any desired organic solvent for preparing the secondary polyacrylate dispersion B ₁ ) is suitable. These solvents may be used in any desired amount, but preferably in amounts of less than 20 wt% based on the sum of the monomers. At least one hydrophobic solvent such as solvent naphtha, toluene, xylene, Kristalloel and at least one hydrophilic solvent such as butyl glycol, butyl diglycol, diethylene glycol, propylene glycol monomethyl ether or dipropylene glycol monomethyl A solvent mixture of ethers is preferred.

Potential ionic groups, especially carboxyl groups, incorporated into the copolymer are typically neutralized using suitable tertiary amines. Examples of suitable neutralized amines include tertiary monoamines such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, dimethylcyclohexylamine, N-methylmorpholine, N- N-methylpiperidine, N-ethylpiperidine, tertiary diamines such as 1,3-bis (dimethylamino) propane, 1,4-bis (dimethylamino) Or tertiary amines having groups reactive with isocyanates such as alkanolamines such as dimethylethanolamine, methyldiethanolamine, 2-aminomethyl-2-methylpropanol or triethanolamine.

The secondary polyacrylate dispersions B ₁ ) can be prepared by any known prior art process, for example, in a feed process, a batch process or a cascade process.

After the copolymer solution is dispersed in water, the solvent used can be removed proportionally or completely by distillation.

The pH of secondary polyacrylate dispersions B ₁ ) suitable for the coating compositions of the present invention is preferably from 5 to 11, more preferably from 6 to 10.

The solids content of the secondary polyacrylate dispersion B ₁ ) is preferably 20 to 60 wt%, more preferably 35 to 55 wt%, and the average particle size is generally 20 to 400 nm.

In the preparation of the secondary polyacrylate dispersion, what is termed a reactive diluent may be used in place of or in conjunction with a solvent. Suitable reactive diluents include, for example, polyethers having a functionality of 2 and / or 3, which are liquid at room temperature, low viscosity polyesters such as 1 mol of dicarboxylic acids such as dimer fatty acids or adipic acid and 2 mol Of the diol or triol or 2 mol of the glycidyl ester of versatate. Examples of further suitable reactive diluents include reaction products of? -Caprolactone with low molecular weight alcohols, and also hydroxy-functional oils such as castor oil.

Suitable aqueous polymer dispersions B) for the coating compositions of the present invention are also referred to, for example, as hydroxy-functional primary polyacrylate dispersions B ₂ ), which can be prepared in a direct aqueous emulsion state with a suitable surface- By copolymerization of an olefinically unsaturated monomer having a hydroxyl group and an olefin-based monomer having no hydroxyl group in the presence of a hydroxyl group-containing monomer.

Suitable primary polyacrylate dispersions B ₂ ) and their preparation are described, for example, in the literature (RO Athey jr., Emulsion Polymer Technology, Dekker, New York, 1991).

The monomers suitable for preparing the primary polyacrylate dispersions B ₂ ) include, in principle, the monomers already mentioned above in connection with the preparation of the secondary polyacrylate dispersions B ₁ ).

The primary polyacrylate dispersions B ₂ ) are prepared in the presence of a suitable surface-active material. This is a known ionic and / or non-ionic emulsifier per se.

The ionic emulsifier is, for example, a carboxylate group or preferably one having a sulfate, sulfonate, phosphate or phosphonate group. Particularly preferred ionic emulsifiers are composed of long chain alcohols or substituted phenols and also ethylene oxide chains and terminal sulfuric acid monoester groups or terminal phosphoric acid monoester and diester groups having a degree of polymerization of 2 to 100 and preferably neutralized with ammonia . It can be added individually or in any desired mixture state to the emulsion batch.

Nonionic emulsifiers which are usually used in combination with the abovementioned anionic emulsifiers are exemplified by the reaction products of carboxylic acids, alcohols, phenol derivatives and / or amines with epoxides such as ethylene oxide. Suitable nonionic emulsifiers include, for example, the reaction of ethylene oxide with carboxylic acids such as lauric acid, stearic acid, oleic acid, castor oil, carboxylic acid, or abietic acid, relatively long chain alcohols such as oleyl alcohol , Lauryl alcohol or stearyl alcohol, reaction with a phenol derivative such as a substituted benzylphenyl, phenylphenol or nonylphenol, or by reaction with a relatively long chain amine such as dodecylamine or stearylamine , Oligo- ethers and polyethers having a degree of polymerization of from 2 to 100, preferably from 5 to 50,

In the preparation of the primary polyacrylate dispersions B ₂ ), the type of emulsifier of the type mentioned is preferably added in an amount of from 0.1 to 10 wt%, based on the amount of the unsaturated monomers used.

In emulsion polymerization, the polymerization initiator is generally introduced into the initial charge and / or added at the same time, for example, if appropriate, pre-supplied or later supplied and / or extended feed. Examples of suitable initiators are oxidation-reduction systems, peroxides, persulfates and / or azo compounds such as dibenzoyl peroxide, dicumen peroxide, cumene hydroperoxide, potassium peroxodisulfate, ammonium peroxodisulfate, azobis Isobutyronitrile or di-tert-butyl peroxide.

Hybrid forms of polyacrylate dispersions known per se, such as, for example, polyester-polyacrylate dispersions B ₃ , are likewise suitable as aqueous polymer dispersions B) for the coating compositions of the present invention. These dispersions contain both a polyacrylate segment and a polyester segment, and in the presence of a polyester component, which is a reaction that can be carried out, for example, in bulk, preferably in the form of an organic solution, (Co) polymerization of monomers of the type mentioned in connection with the preparation of dispersions B ₁ ). Suitable polyester component is described as a possible synthesis component for the preparation of a polyurethane dispersion B ₄₎ below.

Polyester-polyacrylate dispersions B ₃ ) suitable as aqueous polymer dispersions B) are preferably present in an amount of from 10 to 75 wt%, more preferably from 20 to 60 wt%, based on the total solids content of the dispersion, Lt; / RTI >

A polyurethane dispersion B ₄₎ are also suitable as an aqueous polymer dispersion, B) for the coating compositions of the present invention. These dispersions are common self-emulsifying polyurethanes or polyurethane-polyureas in their aqueous form, known per se.

Self-emulsifying polyurethanes contain ionic and / or non-ionic hydrophilic groups in the polymer chain, which groups can be incorporated directly into the polymer chain, or pendent or incorporated at the ends.

Suitable polyurethane dispersions B ₄₎ is by methods known to those of ordinary skill, it may be made of a polyurethane or polyurethane prepolymer in the melt or organic solution, and then obtained by dispersing it in water, increasing the molecular weight, optionally It is possible to carry out the chain extension reaction in the organic solution state simultaneously with the dispersion step or after the dispersion step.

In the preparation of suitable polyurethane dispersions B _4), the incorporation of hydrophilic groups into the polyurethane is reactive for isocyanate groups using potentially ionic and / or non-ionic variety of compounds, for example, hydroxycarboxylic acids It is possible to use acids such as dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid, hydroxypivalic acid or a mixture of these acids, aminocarboxylic acid Such as isophoronediamine or Michael adduct of ethylenediamine on acrylic acid, aminosulfonic acid such as aminoethyl ethanesulfonic acid, hydroxy- or amino-functional phosphonic acid and / or a molecular weight of from 350 to 2500 g / mol , ≪ / RTI > 1-, 2- or 3-functional polyethylene oxide units, and it is also possible to use mixtures of such compounds.

Particularly suitable hydrophilic monomers include dimethylol propionic acid, dimethylol butyric acid, mono- or dihydroxy-functional polyethylene oxide monomers in the molecular weight range mentioned above, and also hydroxy-functional or amino-functional sulfonic acids and / or Lt; / RTI >

Tertiary amines and / or tertiary amino alcohols, such as those described as neutralizing amines for the secondary polyacrylate dispersions B ₁ ), which are suitable for this purpose, preferably serve as neutralizing agents for these hydrophilic units.

Suitable polyurethane dispersions B ₄ ) are, for example, any desired aliphatic, cycloaliphatic, araliphatic and / or cycloaliphatic compounds of the kind mentioned as starting compounds for the preparation of thioaloponates of component A) And / or aromatic di- and / or polyisocyanates.

It is preferable to use isophorone diisocyanate, 4,4'-diisocyanato-dicyclohexylmethane and / or hexamethylene diisocyanate.

A further synthetic component for preparing suitable polyurethane dispersions B ₄ ) is a polyester of a molecular weight range from 500 to 18,000 g / mol, having a functionality of from 1 to 5, preferably from 2 to 2.5, a polyester amide, , Polyethers, polysiloxanes and / or polycarbonate polyols.

Polyester polyols suitable for preparing polyurethane dispersions B ₄ ) are, for example, aliphatic, cycloaliphatic or aromatic dicarboxylic acids and / or polycarboxylic acids and / or their anhydrides, for example, , Succinic acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, succinic acid, azelaic acid, nonanedicarboxylic acid, decanedicarboxylic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, trimellitic acid, phthalic anhydride , Tetrahydrophthalic acid, maleic acid, maleic anhydride, fumaric acid, dimer and trimer fatty acids, dimethyl terephthalate and bisglycol terephthalate and polyhydric alcohols such as 1,2-ethanediol, 1,2 - and 1,3-propanediol, isomeric butanediol, pentanediol, hexanediol, heptanediol and octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2- and 1,4-cyclohexane Diol, 1,4-cyclohexanedimethanol, 4,4 '- (1-methylethyl Diethylene glycol, tetraethylene glycol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,2,3-propanetriol, Trimethylolethane, 1,1-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 2,2-bis (hydroxymethyl) Has an average functionality of 1.5 to 5, as can be prepared in a known manner by the reaction of 3,5-tris (2-hydroxyethyl) isocyanurate.

Suitable polyester polyols are, for example, lactones as starting molecules and single polyhydric alcohols, such as those exemplified above, which can be prepared in conventional manner, accompanied by ring opening. Examples of lactones suitable for preparing these polyester polyols include? -Propiolactone,? -Butyrolactone,? - and? -Valerolactone,? -Caprolactone, 3,5,5- and 3,3, 5-trimethylcaprolactone or any of the above-mentioned desired mixtures of lactones.

Suitable polycarbonate polyols for preparing polyurethane dispersions B ₄ ) are in particular those which are exemplified in the list of dihydric alcohols, for example polyhydric alcohols mentioned above, diaryl carbonates such as, for example, , Diphenyl carbonate, dimethyl carbonate or phosgene itself. Further suitable polycarbonate polyols are those which additionally contain an ester group as well as a carbonate structure. This is particularly the case, for example, by the teaching of DE-B 1 770 245 with the reaction of a dihydric alcohol with a lactone such as epsilon -caprolactone in particular, and the subsequent reaction of the resulting polyester diol with diphenyl or dimethyl carbonate Lt; / RTI > is a polyester carbonate diol known per se, of the kind obtainable by the reaction. Likewise suitable polycarbonate polyols are those containing ether groups in addition to the carbonate structure. This is especially the case with the known polyether carboxylic acids of the kind obtainable, for example, by the catalytic reaction of alkylene oxides with carbon dioxide in the presence of H-functional starting molecules by the method of EP-A 2046861 Lt; / RTI >

Suitable polyether polyols for preparing polyurethane dispersions B ₄ ) are, for example, those obtainable in a manner known per se by alkoxylation of suitable starting molecules. To prepare these polyether polyols, it is possible to use any of the kinds of polyhydric alcohols desired as starting molecules, for example those of the kind described above for the production of polyester polyols having a molecular weight range of 62 to 400. Suitable alkylene oxides for the alkoxylation reaction are especially ethylene oxide and propylene oxide which may be used in any order or in admixture in an alkoxylation reaction. In addition, similarly suitable polyether polyols can be obtained by polymerizing tetrahydrofuran in the presence of a number average of from 400 g / mol to 4000 g / mol, obtainable, for example, by polymerization of tetrahydrofuran according to the literature (Angew. Chem. 72, 927 Polytetramethylene ether glycol having a molecular weight.

In order to prepare suitable polyurethane dispersions B ₄ ), it is additionally possible to use block copolymers based on the mentioned polyols, for example polyether / polyester copolymers, polycarbonate / polyester copolymers or polycarbos It is also possible to use nate / polyether copolymers.

Preferred polyols for preparing the suitable polyurethane dispersion B ₄₎ is a polyester polyol, a polycarbonate polyol and / or C3 and / or C4 polyether polyol.

In the preparation of suitable polyurethane dispersions B ₄ ) it is also possible to use low molecular weight alcohols optionally having a functionality of from 2 to 4. This is especially true for compounds having a molecular weight of < 500 g / mol, for example simple polyhydric alcohols of the type mentioned above as synthetic components for polyester polyols, or amino alcohols such as diethanolamine, Amine, diisopropanolamine, propanolamine, which may optionally also be present in the ethoxylated and / or propoxylated form and also as any desired mixture of said alcohols.

Generally speaking, when preparing suitable polyurethane dispersions B ₄ ), known compounds as chain extenders are used. These chain extenders are, in particular, diamines, polyamines and / or amino alcohols such as diethanolamine, 1,2-diaminopropane, 1,4-diaminobutane, 2,5-diamino- Hexane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11 -Diaminododecane, 1,12-diaminododecane, triaminononane, ethylenediamine, isophoronediamine, diethylenetriamine, hydrazine, adipic dihydrazide, hydroxyethylethylenediamine, bishydroxyethyl Ethylenediamine, aminopropanol, aminoalkoxysilane, and any desired mixture of such compounds.

Suitable polyurethane dispersions B ₄₎ may be prepared using a suitable solvent. Examples of suitable solvents are acetone, methyl ethyl ketone, N-methyl pyrrolidone and / or N-ethyl pyrrolidone.

Suitable polyurethane dispersions B ₄₎ are conventional catalysts in polyurethane chemistry for accelerating the reaction or to achieve specific effects, such as dibutyl tin dilaurate, dibutyl tin oxide, tin di-octoate, tin chloride, and / Or using a tertiary amine.

Usually, in the preparation of polyurethane dispersions in the melt or organic solution state, diisocyanates and / or polyisocyanates react with polyols and hydrophilic units of the type mentioned to form isocyanato-functional prepolymers, It is then further reacted with a chain extender of the type mentioned in the form of a melt, organic solution or aqueous dispersion to form a high molecular weight polyurethane dispersible and / or dispersible in water.

Any solvent used may be removed in whole or in part by distillation optionally after dispersion.

B suitable polyurethane dispersions in coating compositions of the present invention, ₄₎ preferably have an average particle size of 25 to a solids content of 60 wt%, 5.5 pH value of the to 11 and 20 to 500 ㎚.

Additional aqueous polymer dispersions B) suitable for the coating compositions of the present invention are polyester dispersions and polyester solutions B ₅ ) as obtained by dispersing a suitable water-dilutable polyester polyol in water.

Examples of suitable water-dilutable polyester polyols are, for example, those known from the paint technology and have very good pigment wetting and / or pigment affinity qualities, having an acid value in the range of from 25 to 75 mg KOH / g, from 2.5 to 10 wt% , A molecular weight in the range of 750 to 5000 g / mol, and a fatty acid component in an amount of 15 to 50 wt%.

Suitable polyester dispersions and solution B ₅ ) for the coating compositions of the present invention are those described as synthetic components for the production of, for example, polyester polyols, such as polyurethane dispersions B ₄ ), such as acid anhydrides, Such as, for example, by reaction with phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, trimellitic anhydride or pyromellitic anhydride, the reaction being carried out in the presence of an acid anhydride in the presence of a ratio of hydroxyl groups And the reaction is carried out so that the opening of the anhydride and the incorporation into the polyester occur. In this way, a hydroxy-functional and carboxy-functional polyester is obtained, which can be dissolved or dispersed in water after complete or proportional neutralization of the carboxyl groups. Whereby an aqueous polyester dispersion or solution B ₅ ) having an average particle size of from 10 to 200, preferably from 25 to 100 nm, is prepared.

Generally speaking, the aqueous polymer dispersions B) used in the coating compositions of the present invention are hydroxy-functional and / or amino-functional dispersions of the kind mentioned. However, it is also possible to use the non-functional polymer dispersion B) as a binder component in the coating composition of the present invention.

The aqueous polymer dispersion B) used in the coating composition of the present invention preferably comprises at least one aqueous secondary polyacrylate dispersion B ₁ ), a polyester-polyacrylate dispersion B ₃ ) and / or a polyester polyol , Polyurethane dispersions B ₄ based on polycarbonate polyols and / or C ₃ - or C ₄ -polyether polyols.

A hydroxyl group content of 0.5 to 7.0 wt%, preferably 0.5 to 6.0 wt%, more preferably 1.0 to 5.0 wt%, based on the resin solids, of less than 50 mg KOH / g, preferably 40 mg KOH / g Average molecular weight, as determined by gel permeation chromatography, of less than 30 mg KOH / g, and an acid value of from 500 to 30,000, preferably from 1000 to 15,000, more preferably from 1500 to 10,000, The hydroxy-functional aqueous polymer dispersion B) having M _n is preferably used in the coating composition of the present invention.

The coating composition of the present invention optionally comprises at least one catalyst C) for crosslinking the silane group. This type of catalyst is any compound capable of accelerating the hydrolysis and condensation of alkoxysilane groups.

Examples of suitable catalysts C) are acids such as organic carboxylic acids, sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, trifluoroacetic acid, phosphoric acid monoesters and phosphoric acid diesters such as dibutyl phosphate , 2-ethylhexylphosphate, phenylphosphate and bis (2-ethylhexyl) phosphate, and also phosphonic acid diesters and diphosphonic acid diesters, such as those described in WO 2007/033786.

It is also possible to use a base such as N-substituted amidine 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and 1,5-diazabicyclo [5.4.0] undec- DBU) or metal salts and metal chelates such as tetraisopropyl titanate, tetrabutyl titanate, titanium (IV) acetylacetonate, aluminum tri-sec-butoxide, aluminum acetylacetonate, aluminum triflate, Or zirconium ethylacetoacetate, such as those described in WO 2006/042658, are likewise suitable as catalysts C).

Other suitable catalysts C) are phosphoric acid esters and phosphonic acid esters of the type mentioned above, which are present in the form blocked with an amine, preferably a tertiary amine. Particularly preferred catalysts of this type are those which release acidic phosphoric acid and phosphonic acid esters again accompanied by the removal of blocking amines in the temperature range of from 100 to 150 &lt; 0 &gt; C, which represent active active catalysts. Suitable amine-blocked phosphoric acid catalysts C) are described, for example, in WO 2008/074489 and WO 2009/077180.

Likewise suitable catalysts C) are used in blocked form, for example in the amine-neutralized form, or as adducts with epoxides as described in DE 2 356 768 B1, and release catalytic sulfonic acids again above 100 ° C &Lt; / RTI &gt; of the above-mentioned type.

Further catalysts C) suitable for crosslinking the silane group are also tetraalkylammonium carboxylates such as, for example, tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetra Methyl ammonium benzoate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate Tetrabutylammonium acetate, tetrabutylammonium butyrate, tetrabutylammonium butyrate, tetrabutylammonium butyrate, tetrabutylammonium butyrate, tetrabutylammonium butyrate, tetrabutylammonium butyrate, Ammonium benzoate.

Suitable catalysts C) for the crosslinking of silane groups can also be prepared from quaternary ammonium and phosphonium polyamides as known, for example, from EP-A 0 798 299, EP-A 0 896 009 and EP-A 0 962 455 as trimerization catalysts for isocyanate groups, Fluoride.

Finally, suitable catalysts C) are also zinc-amidine complexes which can be prepared by the process of WO 2014/016019 by reaction of amidine with at least one zinc (II) biscarboxylate.

Catalysts C) which are preferred for crosslinking the silane groups are acidic phosphate esters, phosphonic acid esters and sulfonic acid esters of the mentioned type which may optionally be present in the form blocked with an amine, and also tetraalkylammonium carboxylates of the type mentioned. Particularly preferred catalysts C) are amine-blocked phosphoric acid esters and sulfonic acids, and also the tetraalkylammonium carboxylates mentioned. Particularly preferred catalysts C) are amine-blocked phenylphosphates and bis (2-ethylhexyl) phosphate, tetraethylammonium benzoate and tetrabutylammonium benzoate.

In addition to the catalysts C) illustrated above for silane crosslinking, the coating compositions of the present invention optionally comprise a urethane-forming catalyst, such as, for example, a urethane- And examples of such catalysts include tertiary amines such as triethylamine, pyridine, methylpyridine, benzyldimethylamine, N, N-endoethylenepiperazine, N-methylpiperidine, N, N'-dimethylpiperazine or a metal salt such as iron (III) chloride, zinc chloride, zinc 2-ethyl caproate, tin (II) octanoate, Tin (II) ethyl caproate, dibutyltin (IV) dilaurate, zirconium (IV) isopropoxide, zirconium (IV) n-butoxide, zirconium Bismuth (III) 2- Butyl hexanoate, bismuth (III) octoate, the mole rib deneom glycolate and / or lithium molybdate.

Catalyst C) may optionally be present in the coating composition of the invention either as a separate material or in the form of any desired mixture with one another, such that the total solids content of the polyisocyanate component A) and the solids content of the hydroxy-functional binder component B) , Preferably not more than 2 wt%, more preferably not more than 1 wt%, calculated as the sum of all the catalysts C) used, based on the weight of the catalyst.

The coating composition of the present invention may optionally comprise further auxiliaries and additives D). This can be achieved, in particular, by the addition of auxiliaries and additives known to the ordinarily skilled artisan from aqueous coating techniques, such as, for example, solvents, UV stabilizers, antioxidants, flow control agents, rheological additives, slip additives, defoamers, dispersion aids, thickeners, Dyes, quenchers, flame retardants, hydrolysis inhibitors, disinfectants, binders, water scavengers, viscoelastic modifiers, wetting agents, demixers, adhesion promoters, fillers and / or pigments.

For example, a paint solvent described as an organic solvent D ₁ ), for example, a solvent for optional use in the production of a thioalophanate containing a silane group, can be added to the coating composition of the present invention. As a solvent added to the polyisocyanate component A), for example to further reduce viscosity and facilitate incorporation into the aqueous phase, a suitable solvent is preferably a solvent which is chemically inert to the isocyanate and silane groups of the polyisocyanate component A) And has a water content of at most 1.0 wt%, more preferably at most 0.5 wt%, based on the solvent used.

Suitable UV stabilizers D ₂ ) are preferably selected from piperidine derivatives such as, for example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy- Pentamethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl- (2,2,6,6-tetramethyl-4-piperidyl) butyrate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Dodecanedioate; Benzophenone derivatives such as 2,4-dihydroxy-, 2-hydroxy-4-methoxy-, 2-hydroxy-4-octoxy-, 2-hydroxy- , 2'-dihydroxy-4-dodecyloxy-benzophenone; Benzotriazol-2-yl) -6-dodecyl-2, 4-di-tert-pentylphenol, 2- (2H- Methylphenyl) phenol, 2- (5-chloro-2H-benzotriazol-2-yl) (1,1-dimethylethyl) -4-methylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, isooctyl 3- ( (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenylpropionate) Bis (1, 1-dimethylethyl) phenol, 2- (2H-benzotriazol- Chloro-2H-benzotriazol-2-yl) -4,6-bis (1,1-dimethylethyl) phenol; Oxalanilides such as 2-ethyl-2'-ethoxy- or 4-methyl-4'-methoxyoxanilide; Salicylic esters such as phenyl salicylate, 4-tert-butylphenyl salicylate, 4-tert-octylphenyl salicylate; Methyl-4-methoxy cinnamate, butyl? -Cyano-? -Methyl-4-methoxy cinnamate, ethyl? -Cyano-? -Phenyl cinnamate Mate, isooctyl a-cyano-beta-phenyl cinnamate; And malonic acid ester derivatives such as dimethyl 4-methoxybenzylidene malonate, diethyl 4-methoxybenzylidene malonate, and dimethyl 4-butoxybenzylidene malonate. These preferred UV stabilizers can be used individually or in any combination with each other.

Optionally, at least one of the exemplified UV stabilizers D ₂ ), calculated on the basis of the total amount of solids content of the polyisocyanate component A) and the solids content of the aqueous polymer dispersion B), as a total amount of UV stabilizer used, , Preferably 0.001 to 3.0 wt%, more preferably 0.01 to 2 wt%, based on the total weight of the coating composition.

Suitable antioxidants D ₃ ) are preferably sterically hindered phenols which are preferably selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol (ionol), pentaerythrityl tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis (3-tert- methylphenyl) propionate, 2,2'-thiobis (4-methyl-6-tert-butylphenol) and 2,2'-thiodiethylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. If desired, it can be used individually or in any desired combination with each other.

These antioxidants D ₃ ) are preferably 0.01 to 3.0 wt%, calculated as the total amount of antioxidants used, based on the total solids content of the polyisocyanate component A) and the solids content of the aqueous polymer dispersion B) , And more preferably 0.02 to 2.0 wt%.

In order to prevent premature crosslinking of the silane groups in the coating compositions of the present invention, water quenching agents D ₄ ), for example orthoformic esters such as triethyl orthoformate, or vinyl silanes, such as vinyltrimethoxysilane, It may be advantageous to add to component A). These water scavengers, if used, are used in an amount of 5 wt% or less, preferably 2 wt% or less, based on the polyisocyanate component A).

To improve substrate wetting, the coating compositions of the present invention optionally comprise a suitable flow control agent D ₅ ), such as organo modified siloxanes such as polyether-modified siloxanes, polyacrylates and / or fluorine surfactants . These flow control agents, if used, are used in an amount of up to 3 wt%, preferably up to 2 wt%, more preferably up to 0.05 wt%, based on the total solids content of the polyisocyanate component A) and the solids content of the aqueous polymer dispersion B) To 1.5 wt%.

Examples of fillers suitable for coating compositions of the present invention include granulated stone or granulated plastics, glass beads, sand, cork, chalk or talc. A preferred filler is chalk or talc. Examples of suitable pigments are titanium dioxide, zinc oxide, iron oxide, chromium oxide or carbon black. A general overview of suitable fillers and pigments D) can be found in the literature (" Lehrbuch der Lacke und Beschichtungen, Band II, Pigmente, Fuellstoffe, Farbstoffe ", Kittel, Verlag WA Colomb in der Heenemann GmbH, Berlin-Oberschwandorf, 1974, -265). A preferred pigment used is titanium dioxide.

The exemplified fillers and pigments, if used, are used in an amount of up to 95 wt%, preferably up to 80 wt%, based on the total solids content of the polyisocyanate component A) and the solids content of the aqueous polymer dispersion B) .

It is likewise possible to optionally add further auxiliaries and additives to the coating composition of the invention, such as rheological additives, slip additives, defoamers, dispersion aids, thickeners, emulsifiers, dyes, quenchers, flame retardants, hydrolysis inhibitors, disinfectants, Viscoelastic modifiers, wetting agents, deagglomerating agents, and / or adhesion promoters, if known and used by those of ordinary skill in the art, are used in conventional amounts in the coating arts. A general overview of this type of suitable adjuvants and additives can be found, for example, in Bodo Mueller, &quot; Additive kompakt ", Vincentz Network GmbH & Co KG (2009) or Lehrbuch der Lacke und Beschichtungen, Band III., Loesemittel , Weichmacher, Additive, Zwischenprodukte ", H. Kittel, Verlag WA Colomb in der Heenemann GmbH, Berlin-Oberschwandorf, 1976, pp. 237-398).

The total amount of the further auxiliaries and additives D) is preferably not more than 30 wt%, more preferably not more than 20 wt%, based on the total solids content of the polyisocyanate component A) and the solids content of the aqueous polymer dispersion B) to be.

To prepare an aqueous coating composition, the polyisocyanate component A) is emulsified in an aqueous polymer dispersion B). In this case, the polyisocyanate component A) and the aqueous polymer dispersion B) comprising at least one thiophosphate polyisocyanate containing a silane group are usually prepared by reacting each hydroxyl group of the polymer dispersion B) and / or amino Is used in an amount such that an isocyanate group of from 0.5 to 2.0, preferably from 0.6 to 1.8, more preferably from 0.7 to 1.5, polyisocyanate component A) is present.

In the case of using a non-functional polymer dispersion B), i.e. a dispersion B) which does not have a group reactive with isocyanate, the polyisocyanate component A) is present in a total amount of the polyisocyanate component A) and the polymer dispersion B) Will generally be used in amounts of up to 20 wt%, preferably up to 10 wt%.

The optional catalyst components C) and optionally further auxiliaries and additives D) to be used in conjunction therewith may here be added in any order, successively or together, optionally even before the actual mixing of the reaction components, and the polyisocyanate component A) and / or the aqueous polymer dispersion B), in which case the catalyst component C) is particularly preferably added to the polymer dispersion B) in order to avoid premature silane condensation.

In order to prepare the aqueous coating compositions of the present invention, the components A) to D) can be prepared by conventional dispersion techniques, for example by simple manual stirring, or by means of suitable devices such as, for example, , Bead mill or jet disperser.

Due to the very low viscosity of the thioalophanate containing silane groups present in the polyisocyanate component A), it is possible, for example, in the case of further hydrophilic polyisocyanates being used, for example in a mechanical stirrer, Are merely sufficient to produce a homogeneous coating having generally very good properties.

Surprisingly, according to the studies on which this patent application is based, the coating compositions of the present invention are well suited for the manufacture of coatings such as, for example, paints, sealants and / or adhesives. Using the coating compositions of the present invention, coatings with significantly increased resistance to mechanical scratching and weathering effects compared to known coatings can be produced. Resistance to chemicals is comparable to that of conventional coating compositions. The coating compositions of the present invention are therefore preferably used in applications where severe requirements are placed on the coating in terms of optical quality of the coating and resistance to mechanical scratching.

Accordingly, a further embodiment of the invention relates to the use of the coating compositions according to the invention in the manufacture of polyurethane paints and polyurethane coatings.

A further embodiment of the present invention is a compound of formula

a) applying a coating composition to a substrate; And

b) curing the coating composition

To a method for coating a surface.

The application of the resultant coating composition of the present invention comprising a thioalophanate polyisocyanate containing a silane group as a crosslinking agent is preferably carried out by methods known per se, particularly preferably by spraying, One or more coatings may be applied by spraying, non-pneumatic spraying or electrostatic spraying, for example using one-component or two-component spray units, spreading, rolling, dipping, .

Preferred substrates for the coatings of the present invention are metals, wood and wood-based materials, glass, stone, ceramic materials, mineral building materials such as concrete, hard and soft plastics, textiles, leather and paper. Particularly preferably, the substrate is provided before a coating, a surfacer coating, a basecoat system and / or a clearcoat system with conventional known primers.

The coating composition of the present invention is preferably cured immediately after application or after a predetermined flash-off time has elapsed. The flash-off time is used, for example, for flow and deaeration of the coating film or for evaporation of volatile constituents such as water used and any solvent. The required duration of the flash-off time can be controlled in particular by, for example, application of a temperature rise and / or reduced atmospheric humidity.

The ultimate curing of the applied coating composition of the present invention can finally be accomplished by conventional known methods, at ambient temperature or by heating in an IR lamp or near-infrared (NIR radiation), for example by heating in a forced circulation oven, Preferably from 20 to 200 ° C, more preferably from 30 to 190 ° C, and very preferably from 50 to 180 ° C for a period of from 1 min to 24 h, 12 h, very preferably from 3 min to 8 h.

A further embodiment of the present invention relates to a substrate coated with at least one coating composition of the present invention.

The substrate is preferably selected from the group consisting of metal, wood, wood-based materials, glass, stone, ceramic materials, mineral building materials, hard and soft plastics, fabrics, leather and paper.

The coating is preferably carried out by the method described in this patent specification.

The following examples illustrate the invention. It is not intended to limit the scope of protection of the claims.

<Examples>

All percentages are by weight unless otherwise indicated.

The NCO content was determined by titration according to DIN EN ISO 11909: 2007-05.

The residual monomer content was determined by gas chromatography using internal standards according to DIN EN ISO 10283: 2007-11.

All viscosity measurements were carried out using a PhysicAMCR 51 rheometer from Anton Paar Germany GmbH according to DIN EN ISO 3219: 1994-10 at a shear rate of 250 l / s .

The amount (mol%) of thiourethane, thioalophanate and isocyanurate, the isocyanate subsequent products formed during the preparation of the thioalphonate containing the silane group (starting compound A), was determined using the Bruker DPX- 400 instrument), and it is correlated to the sum of the thiourethane, thioalophanate and isocyanurate groups present in each case &lt; RTI ID = 0.0 &gt; . The chemical shift (in ppm) of the individual structural elements is as follows: thiourethane: 166.8; Thioalophanate: 172.3 and 152.8; Isocyanurate: 148.4.

The gloss of the obtained coating was measured at 20 ° and 60 ° according to DIN EN ISO 2813: 1999-06 using a BYK-Gardner micro-TRI-gloss reflectometer .

The pendulum damping by the Koenig method was determined according to DIN EN ISO 1522: 2007-04 on glass plates.

The wet scratch resistance of the coating was tested by using an Amtec-Kistler laboratory cleaning unit according to DIN EN ISO 20566: 2010-08 and subsequently determining the residual gloss at 20 ° and 60 °.

Resistance to dry scratching was measured using a CM-5 rubbing fastness tester (Atlas Electric Devices Co.) in accordance with DIN EN ISO 105-X12: 2002-12 on 9 μ 281 Q sandpaper By the application of 10 double friction and 9 N force using 3M Deutschland GmbH) and subsequently determining the residual luster at 20 ° and 60 °.

The values for wet scratching and dry scratching are measured immediately after scratching and also after reflow conditions, i.e. as% of residual gloss measured after 2 hours of storage at 60 DEG C, in each case compared to the initial gloss of the coating, Was expressed.

The accelerated weathering test was carried out according to DIN EN ISO 16474/2: 2014-03 Method A, Cycle 1 (102: 18) at Ci5000 weathering ommeter from Atlas Material Testing Technology GmbH.

Preparation of starting material:

The polyisocyanate component A1)

1008 g (6 mol) of hexamethylene diisocyanate (HDI) were introduced under dry nitrogen at a temperature of 80 DEG C with stirring and 196 g (1.0 mol) of mercaptopropyltrimethoxysilane were added over 30 minutes. After about 6 hours, the reaction mixture was further stirred at 80 DEG C until an NCO content of 38.4%, which corresponds to the complete thiourethanization, was reached.

At this point, a sample was taken from the reaction mixture and the composition of the sample was determined using ¹³ C-NMR spectroscopy. According to this analysis, only thiourethane was present. ^The &lt; ¹³ &gt; C-NMR spectrum did not show the signal of thioalophanate or isocyanurate group.

By adding 0.1 g of zinc (II) 2-ethyl-1-hexanoate as a catalyst to the reaction mixture at 80 DEG C, the thioalophanate reaction was initiated, at which point the temperature rose to 85 DEG C . After about 1 hour of catalyst addition, stirring was continued at 85 DEG C until the NCO content fell to 34.9%. The reaction was stopped by adding 0.1 g of orthophosphoric acid and the unreacted monomeric HDI was removed in a thin film evaporator at a temperature of 130 ° C and a pressure of 0.1 mbar. Thus, 538 g of a substantially colorless transparent polyisocyanate mixture having the following characteristics and compositions was obtained.

NCO content: 14.4%

Monomeric HDI: 0.08%

Viscosity (23 ° C): 291 mPas

Thiourethane: 0.0 mol%

Thioalophanate: 91.2 mol%

Isocyanurate group: 8.8 mol%

The polyisocyanate component A2)

1008 g (6 mol) of hexamethylene diisocyanate (HDI) were introduced under dry nitrogen at a temperature of 80 DEG C with stirring and 0.1 g of zinc (II) 2-ethyl-1-hexanoate was added as a catalyst. Over a period of about 30 minutes, 196 g (1.0 mol) of mercaptopropyltrimethoxysilane was added dropwise, at which time the temperature of the mixture rose to 85 DEG C due to the initiation of exothermic reaction. After about 2 hours, the reaction mixture was further stirred at 85 [deg.] C until the NCO content fell to 34.9%. The catalyst was deactivated by addition of 0.1 g of orthophosphoric acid and the unreacted monomeric HDI was removed in a thin film evaporator at a temperature of 130 ° C and a pressure of 0.1 mbar. Thus, 523 g of a substantially colorless transparent polyisocyanate mixture having the following characteristics and compositions was obtained.

NCO content: 14.2%

Monomeric HDI: 0.05%

Viscosity (23 ° C): 249 mPas

Thiourethane: 0.0 mol%

Thioalophanate: 98.5 mol%

Isocyanurate group: 1.5 mol%

Polyisocyanate component A3)

According to the process described for the polyisocyanate component B 2), 1344 g (8 mol) of HDI are reacted with 196 g of mercaptopropyltrimethoxysilane in the presence of 0.15 g of zinc (II) 2-ethyl-1-hexanoate 1.0 mol) at 85 DEG C until the NCO content reached 38.2%. After the reaction was terminated with 0.15 g of orthophosphoric acid and the reaction mixture was worked up by distillation in a thin-film evaporator, 528 g of a substantially colorless clear polyisocyanate mixture of the following characteristics and compositions was obtained:

NCO content: 15.2%

Monomeric HDI: 0.12%

Viscosity (23 ° C): 209 mPas

Thiourethane: 0.0 mol%

Thioalophanate: 99.0 mol%

Isocyanurate group: 1.0 mol%

Polyisocyanate component A4)

According to the process described for the polyisocyanate component B 2), 672 g (4 mol) of HDI are reacted with 196 g of mercaptopropyltrimethoxysilane in the presence of 0.1 g of zinc (II) 2-ethyl-1-hexanoate 1.0 mol) at 85 DEG C until the NCO content reached 29.0%. After post-treatment by stopping the reaction with 0.1 g of orthophosphoric acid and distilling the reaction mixture in a thin-film evaporator, 486 g of a substantially colorless transparent polyisocyanate mixture having the following characteristics and compositions was obtained.

NCO content: 12.9%

Monomeric HDI: 0.06%

Viscosity (23 ° C): 298 mPas

Thiourethane: 0.0 mol%

Thioalophanate: 98.3 mol%

Isocyanurate group: 1.7 mol%

Polyisocyanate component A5)

According to the process described for the polyisocyanate component B 2), 756 g (4.5 mol) of HDI are reacted with 294 g of mercaptopropyltrimethoxysilane in the presence of 0.1 g of zinc (II) 2-ethyl-1-hexanoate 1.5 mol) at 85 DEG C until the NCO content reached 24.0%. After post-treatment by stopping the reaction with 0.1 g of orthophosphoric acid and distilling the reaction mixture in a thin-film evaporator, 693 g of a substantially colorless clear polyisocyanate mixture of the following characteristics and compositions was obtained:

NCO content: 11.8%

Monomeric HDI: 0.06%

Viscosity (23 ° C): 452 mPas

Thiourethane: 0.0 mol%

Thioalophanate: 99.0 mol%

Isocyanurate group: 1.0 mol%

Silane group _{content: 25.9% (-Si (OCH 3} ) calculated as _3; molecular weight = 121 g / mol)

Polyisocyanate component A6)

According to the process described for the polyisocyanate component B 2), 756 g (4.5 mol) of HDI are reacted with 357 g of mercaptopropyltriethoxysilane in the presence of 0.1 g of zinc (II) 2-ethyl-1-hexanoate 1.5 mol) at 85 DEG C until the NCO content reached 22.6%. After post-treatment by stopping the reaction with 0.1 g of orthophosphoric acid and distilling the reaction mixture in a thin-film evaporator, 715 g of a substantially colorless transparent polyisocyanate mixture of the following characteristics and compositions was obtained:

NCO content: 11.3%

Monomeric HDI: 0.21%

Viscosity (23 ° C): 267 mPas

Thiourethane: 0.0 mol%

Thioalophanate: 98.4 mol%

Isocyanurate group: 1.6 mol%

Polyisocyanate component A7)

504 g (3.0 mol) of HDI were introduced under dry nitrogen at a temperature of 80 DEG C with stirring, and 588 g (3.0 mol) of mercaptopropyltrimethoxysilane was added over 30 minutes. After about 12 hours, the reaction mixture was further stirred at 80 [deg.] C until an NCO content of 11.5% corresponding to the complete thiourethanization was reached. 0.1 g of zinc (II) 2-ethyl-1-hexanoate as catalyst was added to the reaction mixture at 80 ° C, at which time the temperature rose to 85 ° C due to the initiation of the thioalophanated exothermic reaction. After about 4 hours of addition of the catalyst, the mixture was further stirred at 85 [deg.] C until the NCO content fell to 3.0%. Subsequently, the reaction was stopped by adding 0.1 g of orthophosphoric acid. Thus, a substantially colorless transparent polyisocyanate mixture having the following characteristics and compositions was obtained.

NCO content: 3.0%

Monomeric HDI: 0.69%

Viscosity (23 ° C): 9220 mPas

Thiourethane: 23.2 mol%

Thioalophanate: 66.6 mol%

Isocyanurate group: 10.2 mol%

Polyisocyanate component A8)

1332 g (6 mol) of isophorone diisocyanate (IPDI) were introduced under dry nitrogen at a temperature of 95 캜 with stirring and 0.2 g of zinc (II) 2-ethyl-1-hexanoate was added as a catalyst. Over a period of about 30 minutes, 196 g (1.0 mol) of mercaptopropyltrimethoxysilane was added dropwise, at which time the temperature of the mixture rose to 103 캜 due to the initiation of exothermic reaction. After about 5 hours, the reaction mixture was further stirred at 100 &lt; 0 &gt; C until the NCO content fell to 27.4%. The catalyst was deactivated by addition of 0.2 g of orthophosphoric acid and the unreacted monomer IPDI was removed in a thin film evaporator at a temperature of 160 ° C and a pressure of 0.1 mbar. Thus, 659 g of a pale yellow transparent polyisocyanate mixture having the following characteristics and compositions was obtained.

NCO content: 11.6%

Monomeric IPDI: 0.46%

Viscosity (23 ° C): 11,885 mPas

Thiourethane: 1.3 mol%

Thioalophanate: 93.4 mol%

Isocyanurate group: 4.3 mol%

Polyisocyanate component A9)

756 g (4.5 mol) of HDI were mixed in a dropwise manner with 196 g (1.0 mol) of mercaptopropyltrimethoxysilane over a period of about 30 minutes while stirring under dry nitrogen at a temperature of 80 캜. Subsequently, the reaction mixture was heated to 140 DEG C and after about 5 hours, further stirring was carried out until the NCO content dropped to 24.0%. After distillation in a thin-film evaporator, 685 g of a substantially colorless transparent polyisocyanate mixture having the following characteristics and compositions was obtained.

NCO content: 11.8%

Monomeric HDI: 0.08%

Viscosity (23 ° C): 447 mPas

Thiourethane: 0.0 mol%

Thioalophanate: 98.6 mol%

Isocyanurate group: 1.4 mol%

The polyisocyanate component A10) -A13) and the comparative polyisocyanate C1)

80 parts by weight of a low-monomer-content polyisocyanurate polyisocyanate based on HDI having an NCO content of 21.6%, an average isocyanate functionality of 3.5 and a viscosity (23 DEG C) of 3200 mPas were mixed with a thioalophanate polyisocyanate A5) 20 parts by weight, and homogenized by stirring at 60 DEG C for 30 minutes to obtain a silane-functional polyisocyanate mixture A10). In the same manner, silane-functional polyisocyanate mixtures A11) to A13) were prepared using the same starting components in the amounts listed in Table 1 below.

For comparison, reference is made to Example 1 of WO 2009/156148 to determine the amount of low-monomer-content polyisocyanurate based on HDI described above in the presence of 500 ppm of dibutyltin dilaurate as catalyst at &lt; RTI ID = 79 parts by weight of a polyisocyanate (NCO content: 21.6%, average NCO functionality: 3.5; viscosity (23 ° C): 3200 mPas) and 21 parts by weight of mercaptopropyltrimethoxysilane were reacted without solvent to obtain a partially silanized HDI trimer (Comparative polyisocyanate C1).

Table 1 below shows the composition (parts by weight) and characteristics of the silane-functional polyisocyanate mixtures A10) to A13) and also the characteristics of the comparative polyisocyanates C1) according to WO 2009/156148.

Table 1:

13% of the silane group content (-Si (OCH ₃₎ calculated as _3; molecular weight = 121 g / mol) having a silane-functional polyisocyanate mixture A13) and comparison polyisocyanate according to WO 2009/156148 C1) , The distinct advantages of the silane-functional thioalophanate polyisocyanate compared to the prior art in terms of isocyanate content, isocyanate functionality and viscosity have been very impressively demonstrated.

Comparative polyisocyanate C2) (silane group-free)

Prepared by trimerization of HDI using a 50% solution of tetrabutylphosphonium hydroxide difluoride in isopropanol / methanol (2: 1) as catalyst according to Example 4 of EP-A 0 962 455, HDI polyisocyanate containing a maleurate and an iminooxyadiazideione group. The reaction was stopped by adding dibutyl phosphate when the NCO content of the crude mixture was 43%. Subsequently, the unconverted HDI was removed via thin-film distillation at a temperature of 130 ° C and a pressure of 0.2 mbar.

NCO content: 23.4%

NCO functionality: 3.2

Monomeric HDI: 0.2%

Viscosity (23 ° C): 700 mPas

Isocyanurate: 49.9 mol%

45.3 mol% of iminooxadiazide &lt; RTI ID = 0.0 &gt;

Uretdione 4.8 mol%

Examples 1 and 2 (invention and comparison)

Can have an OH content of 42% solids content and 5.0% based on the resin solid name Bay hydroxide roll (Bayhydrol) ^® A 2695 obtained under (Bayer meoteo real Science AG (Bayer MaterialScience AG), Leverkusen material), a commercial aqueous hydroxide 100 parts by weight of a hydroxy-functional polyacrylate dispersion were mixed with 0.21 part by weight of a commercial silicone surface-active agent (Byk-349, Byk Chemie GmbH), a commercial silicone surface additive (BI- 0.44 part by weight of a 10% aqueous solution of a commercial thickener (Novec FC-4430, 3M Deutschemie GmbH) and 0.44 part by weight of a commercial thickener (Borch Gel, PW 25, OMG Borchers GmbH), and diluting the mixture with 14.0 parts by weight of water.

To this batch, 88.2 parts by weight of a 65% solution of a silane-group-containing thioalophanate A5 in MPA, 50% by weight of a commercial UV absorber (Tinuvin 348-2, BASF SE) in MPA, , And 93.2 parts by weight of a crosslinker solution comprising 1.3 parts by weight of an isocyanate group to an alcoholic hydroxyl group of 1.3: 1, consisting of 2.0 parts by weight of a 50% solution of a commercial radical scavenger (Tinuvin 292, BASF) in MPA ) Was added and the mixture was homogenized by stirring at 1000 rpm for 5 minutes.

For comparison, in the same way, 65% solution 44.5 parts by weight of the bay hydroxide roll ^® A 2695 100 parts by weight of the blended paint layout, such an arrangement compared the polyisocyanate C2 of MPA) from using the additives specified above, MPA 2.1 parts by weight of a 50% solution of a commercial commercial UV absorber (Tinuvin 348-2, BASF) and 0.9 parts by weight of a 50% solution of a commercial radical scavenger (Tinuvin 292, BASF) in MPA Corresponding to an equivalent ratio of an isocyanate group to an alcoholic hydroxyl group of 1.3: 1).

The service life of the two coating compositions prepared in this manner was about 2 hours in each case.

To determine the pendulum damping, two coating compositions were applied to a glass plate with a film thickness of 60 mu m using a four-way applicator, respectively, and in each case, under forced conditions (30 min / 60 DEG C ) For 15 minutes and then dried at room temperature (about 20 &lt; 0 &gt; C).

Scratch resistance was tested for a complete multi-coat paint system. For this purpose, the inventive coating composition and the comparative coating composition were coated in a commercially available one-component OEM water-based sealer and a conventional black one-component OEM water-based basecoat Lt; / RTI &gt; coated aluminum panel.

Table 2 below shows a comparison of the performance test results.

Table 2:

As a result of the comparison, the coating film obtained from the coating composition of the present invention was found to have a much higher residual gloss than the crosslinked coating material using a standard polyisocyanate directly after wet scratching. In the case of dry scratching, both coating films initially exhibited similarly significant loss of gloss, but under the reflow conditions, the coating material of the present invention substantially restored its original gloss. Moreover, in the accelerated weathering test, the coating material of the present invention is excellent in that it maintains much better gloss and less yellowing.

Claims (15)

A) at least one polyisocyanate component,
B) at least one aqueous polymer dispersion,
C) optionally at least one catalyst for crosslinking the silane group and
D) optionally further auxiliaries and additives
Wherein the polyisocyanate component A) comprises at least one thiophosphate containing silane groups of the formula (I) &lt; EMI ID = 15.1 &gt;

here,
R ¹ , R ² and R ³ are the same or different radicals and are saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals each having up to 18 carbon atoms, May contain up to three heteroatoms from the oxygen, sulfur and nitrogen series,
X is a linear or branched organic radical having at least two carbon atoms,
Y is a linear or branched, aliphatic or cycloaliphatic, araliphatic or aromatic radical having up to 18 carbon atoms,
n is an integer of 1 to 20; The composition of claim 1, wherein the polyisocyanate component A)
R ¹ , R ² and R ³ are the same or different radicals, saturated, linear or branched, aliphatic or cycloaliphatic radicals each having up to 6 carbon atoms, optionally containing up to 3 oxygen atoms ,
X is a linear or branched alkylene radical having from 2 to 10 carbon atoms,
Y and n are as defined in claim 1, at least one thiophosphate containing silane groups of formula (I). The composition of claim 1, wherein the polyisocyanate component A)
R ¹ , R ² and R ³ are each an alkyl radical having 6 or fewer carbon atoms and / or an alkoxy radical containing 3 or fewer oxygen atoms, provided that at least one of the radicals R ¹ , R ² and R ³ is Said alkoxy radical,
X is a propylene radical (-CH ₂ -CH ₂ -CH ₂ -),
Y and n are as defined in claim 1, at least one thiophosphate containing silane groups of formula (I). The composition of claim 1, wherein the polyisocyanate component A)
Wherein R ¹ , R ² and R ³ are the same or different radicals and are each methyl, methoxy or ethoxy, provided that at least one of the radicals R ¹ , R ² and R ³ is a methoxy or ethoxy radical,
X is a propylene radical (-CH ₂ -CH ₂ -CH ₂ -),
Y and n are as defined in claim 1, at least one thiophosphate containing silane groups of formula (I). The composition of claim 1, wherein the polyisocyanate component A)
Characterized in that it comprises at least one thiophosphate containing silane groups of the formula (I), wherein Y is a linear or branched, aliphatic or cycloaliphatic radical having from 5 to 13 carbon atoms. The composition of claim 1, wherein the polyisocyanate component A)
Y is 1,5-diisocyanato pentane, 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4 (I), which is an aliphatic and / or cycloaliphatic radical obtained by removing an isocyanate group from a diisocyanate selected from the family of diisocyanates and / or 4,4'-diisocyanatodicyclohexylmethane. &Lt; / RTI &gt; wherein the coating composition comprises at least one thioallophanate. 7. The composition according to any one of claims 1 to 6, wherein the aqueous polymer dispersion B) comprises at least one of an aqueous or water-dispersible polyacrylate resin, a polyester resin, a polyurethane resin, a polyurea resin, And / or a polyether resin. 8. The composition according to claim 7, wherein the aqueous polymer dispersion B) comprises at least one aqueous secondary polyacrylate dispersion B ₁ ), a polyester-polyacrylate-dispersion B ₃ ) and / or a polyester polyol, A polyurethane dispersion B ₄ ) based on a polyether polyol and / or a C3 and C4 polyether polyol. The coating composition according to claim 7 or 8, wherein the aqueous polymer dispersion B) contains a hydroxyl group and / or an amino group. The coating composition according to claim 9, wherein the catalyst C) comprises at least one amine-blocked acidic phosphate ester, amine-blocked sulfonic acid and / or at least one tetraalkylammonium carboxylate. 10. A process according to claim 9 wherein the catalyst component C) is at least one amine-blocked phosphoric acid phenyl ester, amine-blocked bis (2-ethylhexyl) phosphate ester, tetraethylammonium benzoate and / or tetrabutylammonium benzoate &Lt; / RTI &gt; The individual components A), B), optionally C) and optionally D) are added, in any order, either sequentially or together, to the hydroxyl and / or amino groups of the polymer dispersion B) in an amount of from 0.5 to 2.0, A process for preparing a coating composition according to any one of claims 1 to 11, characterized in that the isocyanate groups of the polyisocyanate component . Use of a coating composition according to any one of claims 1 to 12 in the manufacture of polyurethane paints and coatings. The process according to claim 13, wherein the coating composition is applied at a temperature of from 20 to 200 캜, more preferably from 30 to 190 캜, very preferably from 50 to 180 캜 for a period of from 1 min to 24 h, more preferably from 2 min to 12 h , Very preferably from 3 min to 8 h. &Lt; RTI ID = 0.0 &gt; 5. &lt; / RTI &gt; 12. A substrate coated with a coating composition according to any one of the preceding claims.